Mechanistic insight into rhodium-catalyzed intramolecular enantioselective C-H silylation with dihydrosilanes

Li, Na1,2; Ke, Jie1,2; Ren, Li-Qing1,2; Li, Yingzi1,2; He, Chuan1,2

2023-11-16

10.1016/j.checat.2023.100799

CHEM CATALYSIS   影响因子和分区

2667-1093

Although enantioselective C -H silylation has progressed rapidly in recent years, little mechanistic information on these reactions is available, especially for C -H silylation with dihydrosilanes toward silicon-stereogenic silanes. Here, we report a thorough combined experimental and theoretical mechanistic study on the rhodium-/Josiphos-catalyzed intramolecular enantioselective C -H silylation of dihydrosilanes for the construction of silicon-stereogenic centers. A rhodium silyl dihydride complex was identified as the resting state in the catalytic cycle, which was generated via a facile silyl metal migration process. This key resting state was also synthesized and characterized by X-ray crystallographic analysis. Density functional theory calculations were conducted to elucidate the full picture of the mechanism and shed light on the origin of the observed enantioselectivity and the racemization process in the reaction. With the understanding of the mechanism, both enantioenriched tetraorganosilanes and monohydrosilanes could be synthesized with decent yields and enantiomeric excess, respectively.

ESCI

英语

第一 ; 通讯

National Natural Science Foundation of China["22122102","22101113","22271134"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Guangdong Pearl River Talent Program[2019QN01Y628] ; Shenzhen Science and Technology Innovation Committee[RCJC20221008092723013]

Chemistry

Chemistry, Physical

WOS:001114248300001

CELL PRESS

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China

Li, Na,Ke, Jie,Ren, Li-Qing,et al. Mechanistic insight into rhodium-catalyzed intramolecular enantioselective C-H silylation with dihydrosilanes[J]. CHEM CATALYSIS,2023,3(11).

Li, Na,Ke, Jie,Ren, Li-Qing,Li, Yingzi,&He, Chuan.(2023).Mechanistic insight into rhodium-catalyzed intramolecular enantioselective C-H silylation with dihydrosilanes.CHEM CATALYSIS,3(11).

Li, Na,et al."Mechanistic insight into rhodium-catalyzed intramolecular enantioselective C-H silylation with dihydrosilanes".CHEM CATALYSIS 3.11(2023).